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EP2083044B1 - Composition pour stabiliser des polymères contenant de l'halogène - Google Patents

Composition pour stabiliser des polymères contenant de l'halogène Download PDF

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EP2083044B1
EP2083044B1 EP09151014.9A EP09151014A EP2083044B1 EP 2083044 B1 EP2083044 B1 EP 2083044B1 EP 09151014 A EP09151014 A EP 09151014A EP 2083044 B1 EP2083044 B1 EP 2083044B1
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parts
weight
group
halogen
acid
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EP2083044A1 (fr
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Mario Berna
Gianfranco Sarti
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Reagens SpA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/014—Stabilisers against oxidation, heat, light or ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • the invention concerns a composition for stabilizing halogen-containing polymers, in particular polyvinyl chloride (PVC), and halogenated resins in rigid and plasticized formulations comprising said stabilizing compositions.
  • PVC polyvinyl chloride
  • the stabilizing compositions of the invention confer on the final halogenated resin an excellent thermal stability during working.
  • Halogen-containing polymers must be subjected to temperatures within a more or less wide range around 190oC in order to be worked by known processes, such as moulding, calendaring and extrusion.
  • halogen-containing polymers particularly polyvinyl chloride (PVC)
  • PVC polyvinyl chloride
  • EP1406963 describes the use of fluoroalkanesulphonic acids for stabilizing organic plastics containing chlorine.
  • the use of potassium, sodium and lithium trifluoromethanesulphonic acid salts is described to counteract thermal and photochemical degradation.
  • WO02/092686 proposes a heavy-metal-free stabilizer for rigid or semi-rigid PVC, which comprises, as essential components, zeolites or hydrotalcites treated with perchloric acid or metal perchlorates, a metal carboxylate salt, an organic co-stabilizer group and an antioxidant group.
  • compositions enable heavy metal use to be avoided, the zeolites present therein, however, tend to release water which prevents their use as stabilizers in some rigid or semi-rigid PVC applications.
  • the document EP1395630 describes compositions comprising a salt of a halogen-containing oxyacid of formula M(ClO 4 )k and an organic or inorganic acid or an organic base, wherein the oxyacid contains less than 10% of crystallites having a size greater than 3 micrometres.
  • the composition of EP1395630 comprising sodium perchlorate and calcium hydroxide, proves to be particularly effective in increasing dehydrochlorination time.
  • said composition although producing an increase in stability, is not so satisfactory in maintaining the initial colour, thus occasionally causing the final resin colour to redden.
  • other co-stabilizers have to be added to the composition of EP1395630 , with an evident increase in formulation costs.
  • EP0492803 proposes the use of certain potassium or sodium salts of adipic acid in combination with a metal-based stabilizer, specifically an organotin compound, for stabilizing both rigid and plasticized PVC in order to improve thermal stability during processing determined by using the stabilizer alone.
  • a metal-based stabilizer specifically an organotin compound
  • the object of the present invention is to overcome the problems encountered in known stabilizing systems, while at the same time increasing the effectiveness of those which have proved to be the most reliable.
  • An object of the present invention is hence to improve thermal stability effectiveness during processing of halogen-containing polymers, while maintaining unchanged or indeed increasing the time to degradation during processing, thus conferring to the final product an optimal colour and the maintenance thereof for as long as possible.
  • a further object is to provide thermal stability to halogen-containing polymers in those fields of application that use polymers in both rigid and plasticized formulations, thus reducing costs compared to known formulations.
  • composition for stabilizing halogen-containing polymers comprising:
  • the invention concerns a halogenated resin in rigid or plasticized formulation comprising a halogen-containing polymer and a stabilizing composition of the invention.
  • the invention relates to a halogenated resin in rigid formulation comprising polyvinyl chloride (PVC), more preferably chlorinated polyvinyl chloride (C-PVC), and a stabilizing composition of the invention.
  • PVC polyvinyl chloride
  • C-PVC chlorinated polyvinyl chloride
  • the invention therefore concerns a composition for stabilizing halogen-containing polymers comprising: a) disodium adipate, and b) a compound selected from the group consisting of M(ClO 4 )k and (CF 3 SO 3 ) n M wherein M is selected from the group consisting of H + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Ba 2+ , Zn 2+ , Al 3+ and NH 4 + and k and n are 1, 2 or 3 depending on the valency of M, and wherein b) is not perchlorate of barium.
  • composition according to the invention comprises the salt disodium adipate as essential component for stabilizing the halogen-containing polymer. It is present in the composition in an amount in the range from 0.01 to 5 parts by weight, preferably from 0.02 to 2 parts by weight, per 100 parts by weight of the polymer.
  • the polymer stabilizing composition also comprises at least one compound selected from the group consisting of M(ClO 4 )k and (CF 3 SO 3 ) n M wherein M is selected from the group consisting of H + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Ba 2+ , Zn 2+ , Al 3+ and NH 4 + and k and n are 1, 2 or 3 depending on the Valency of M.
  • M of compound b) of the invention is preferably selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ and Zn 2+ , more preferably M is selected from the group consisting of Na + , K + and Ca 2+ , and still more preferably is sodium.
  • composition of the invention in addition to disodium adipate also comprises M(ClO 4 )k or (CF 3 SO 3 ) n M or both.
  • the composition comprises perchloric acid or a perchlorate salt, more preferably the perchlorate salt of a cation selected from the group consisting of Li + , Na + , K + , Mg 2+ , Ca 2+ and Zn 2+ , being even more preferably the perchlorate salt of sodium.
  • perchloric acid or perchlorate salt preferred for the purposes of the invention, can be used in various forms, for example as salts or aqueous or organic solutions, supported on various materials such as PVC, calcium silicate, zeolites or hydrotalcites or bound to a hydrotalcite by chemical reaction.
  • complexes of metal perchlorate are preferred, more preferably sodium perchlorate, with triethylene glycol, butyldiglycol or polyethylene glycol.
  • the perchloric acid or its salt is preferably included in the composition of the invention in an amount in the range from 0.001 to 2 parts by weight, more preferably from 0.005 to 1 part by weight, per 100 parts by weight of polymer.
  • the stabilizing composition of the invention can comprise (CF 3 SO 3 ) n M as the compound b).
  • (CF 3 SO 3 ) n M is trifluoromethanesulphonic acid or a sodium salt thereof, more preferably it is sodium trifluoromethanesulphonate.
  • composition of the invention can also comprise one or more conventional stabilizers and co-stabilizers, selected from the group consisting of metal soaps, organotin compounds, antioxidants, organic co-stabilizers ( ⁇ -diketones and dihydropyridines or polydihydropyridines, uracil derivatives), alkanolamines, zeolites and hydrotalcites, polyols, hydrates and oxides of alkali and alkaline-earth metals and organic phosphites.
  • conventional stabilizers and co-stabilizers selected from the group consisting of metal soaps, organotin compounds, antioxidants, organic co-stabilizers ( ⁇ -diketones and dihydropyridines or polydihydropyridines, uracil derivatives), alkanolamines, zeolites and hydrotalcites, polyols, hydrates and oxides of alkali and alkaline-earth metals and organic phosphites.
  • composition of the invention preferably comprises one or more stabilizers.
  • the stabilizer is preferably contained in the stabilizing composition of the invention in an amount in the range from 0.05 to 4 parts by weight of halogen-containing polymer.
  • the stabilizers comprised in the composition of the invention are combinations of metal soaps and/or organotin compounds, polyols, antioxidants, organic stabilizers, metal-free stabilizers etc.
  • All metal soaps used as polyvinyl chloride (PVC) stabilizers are suitable for the invention. These are preferably organic salts of sodium, lithium, potassium, calcium, zinc, magnesium, aluminium salts of saturated C 2 -C 22 aliphatic carboxylates, unsaturated C 3 -C 22 aliphatic carboxylates, saturated C 2 -C 22 aliphatic carboxylates substituted with at least one OH group, or whose chain is interrupted by at least one oxygen atom (oxyacids), cyclic or bicyclic carboxylates containing from 5 to 22 carbon atoms, phenylcarboxylates unsubstituted or substituted with at least one OH group and/or substituted with C 1 -C 16 alkyl, naphthylcarboxylates unsubstituted or substituted with at least one OH group and/or substituted with C 1 -C 16 alkyl, phenyl (C 1 -C 16 ) alkylcarboxylates
  • metal salts of monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, n-heptanoic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, palmitic acid, lauric acid, isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl4-hydroxybenzoic acid
  • Metal soaps preferred in the present invention are metal carboxylates of a carboxylic acid containing from 7 to 25 carbon atoms, being typically, benzoates, or alkanoates, and preferably C8-alkanoates, stearates, oleates, laurates, palmitates, behenates, versatates, hydroxystearates, dihydroxystearates, p-tert-butylbenzoates, and 2-ethylhexanoates.
  • a mixture of carboxylates of different structure can also be used as metal soaps. Preference is given to the compositions as aforedescribed containing a zinc and/or calcium soap.
  • Zn, Li, K, Mg, Ca, Na salts of the aforestated fatty acids containing from 7 to 25 carbon atoms are preferably added to the composition of the invention.
  • the aforedescribed metal soaps or metal soap mixture can be present in the composition, preferably, in an amount in the range from 0.05 to 3 parts by weight, more preferably from 0.1 to 1.0 parts by weight, per 100 parts by weight of polymer.
  • Organotin compounds are a particularly well known and extensively used class of metal-containing thermal stabilizers for halogenated vinyl polymers. Compounds containing one or more tetravalent tin atoms, each of which has at least one direct tin-carbon bond, belong to this class.
  • a preferred class of tin-containing thermal stabilizers shows one or more tetravalent tin atoms, each of which has at least one direct tin-oxen or tin-sulphur bond, i.e. containing the group:
  • the organotin compounds preferred in the invention comprise those containing one or more tetravalent tin atoms having at least one direct tin-carbon bond and in which the remaining valencies are satisfied by bonds with oxygen or sulphur, as in the case of a residue resulting from the removal of a hydrogen bound to the sulphur of a mercaptan, mercaptoalcohol, mercaptoacid or mercaptoalcohol ester or as in the case of a residue resulting from the removal of a hydrogen bound to the oxygen of a carboxylic acid or alcohol or hydrohalogen acid, with the proviso that at least one valency is satisfied by a bond with oxygen or sulphur or a mixture of the two.
  • Examples of compounds of this kind are: alkyl tin mercaptides, the product of reacting an organotin halide with a sulphur of an alkali metal and mercaptide, mercaptoacid ester, mercaptoalcohol, mercaptoalcohol ester or mixtures thereof.
  • tin-containing stabilizers included in the present invention is that of compounds not containing sulphur, wherein the tin is bound to oxygen.
  • This group includes, by way of non-limiting example, dibutyltin maleate, dibutyltin di(stearyl maleate), dioctyltin maleate, organotin carboxylates or organotin alkoxides.
  • the stabilizing composition of the present invention can comprise organotin compounds preferably in an amount in the range from 0.1 to 4 parts by weight, more preferably from 0.15 to 2.0 parts by weight, per 100 parts by weight of polymer.
  • metal-free stabilizers esters of ⁇ -aminocrotonic acid can be cited.
  • suitable among these compounds are for example ⁇ -aminocrotonic acid stearyl ester, 1,4 butanediol di( ⁇ -aminocrotonic acid) ester, thio-diethanol- ⁇ -aminocrotonic acid ester.
  • composition of the invention can also comprise other additives able to behave as co-stabilizers, selected from the group consisting of antioxidants, organic co-stabilizers ( ⁇ -diketones and dihydropyridines or polydihydropyridines, uracil derivatives), alkanolamines, zeolites and hydrotalcites, polyols, hydrates and oxides of alkali and alkaline-earth metals and organic phosphites.
  • additives selected from the group consisting of antioxidants, organic co-stabilizers ( ⁇ -diketones and dihydropyridines or polydihydropyridines, uracil derivatives), alkanolamines, zeolites and hydrotalcites, polyols, hydrates and oxides of alkali and alkaline-earth metals and organic phosphites.
  • the organic antioxidants used in the present invention are selected from those already known as additives for plastic materials.
  • preferred are one or more antioxidants selected from the group consisting of alkylidene-bisphenols, esters of ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or poly-alcohols, esters of ⁇ -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly-alcohols, esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or poly-alcohols.
  • antioxidant classes preferred in the invention are examples of antioxidant classes preferred in the invention:
  • antioxidants are comprised preferably in an amount in the range from 0.01 to 1.0 parts by weight, more preferably from 0.1 to 0.5 parts by weight, per 100 parts by weight of polymer.
  • the invention also provides for the optional presence of organic co-stabilizers in the composition of the invention to further increase the effectiveness of the stabilizing composition.
  • organic co-stabilizers optionally present in the stabilizing composition of the invention are preferably one or more compounds selected from: 1) ⁇ -diketonic compounds, 2) dihydropyridines or polydihydropyridines, 3) uracil derivatives.
  • 3-bisdodecyloxycarbonyl-2,6-dimethyl-1,4-dihydropyridine commercially available as Stavinor® D507 and produced by Atochem.
  • Suitable preferred polydihydropyridines are compounds represented by the following formula:
  • Synesal® M thiodiethylene-bis[5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine-3-carboxylate] known commercially as Synesal® M, produced by Lagor.
  • R 1 and R 2 are, each independently of the other, hydrogen, C 1 -C 12 alkyl, C 3 -C 6 alkenyl, C 5 -C 8 cycloalkyl optionally substituted with 1 to 3 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or hydroxyl or with chlorine atoms, or C 7 -C 9 phenylalkyl optionally substituted on the phenol ring with 1 to 3 C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 5 -C 8 cycloalkyl or hydroxyl or with chlorine atoms; Y can be oxygen or sulphur.
  • C 1 -C 4 alkyl examples are methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec-, or tert-butyl.
  • C 1 -C 12 alkyl are, in addition to the aforementioned radicals, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, decyl, undecyl, dodecyl.
  • C 1 -C 4 alkoxy examples are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy.
  • C 5 -C 8 cycloalkyl examples include cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.
  • C 7 -C 9 phenylalkyl examples are benzoyl, 1- or 2- phenylethyl, 3-phenylpropyl, a,a-dimethylbenzyl, or 2-phenylisopropyl, preferably benzyl. If the cycloalkyl or phenyl groups of the phenylalkyl radical are substituted, then they are substituted with one or two substituents, preferably selected from chlorine, hydroxyl, methyl or methoxy.
  • C 3 -C 6 alkenyl examples are allyl, methallyl, 1-butenyl, or 1-hexanyl, preferably allyl.
  • R 1 and R 2 are, each independently of the other, C 1 -C 4 alkyl and hydrogen; in particular, the compound wherein R 1 and R 2 are methyl is preferred.
  • uracil derivatives there can also be optionally present in the composition of the invention oligomeric or polymeric derivatives of formula: wherein
  • the aforedescribed organic antioxidants can be present preferably in an amount in the range from 0.01 to 1.0 parts by weight, in particular from 0.1 to 0.5 parts by weight, per 100 parts by weight of polymer.
  • Alkanolamines advantageously present in the composition of the invention, are compounds of general formula: wherein
  • Examples of preferred alkanolamines according to the general formula are: tri(hydroxyethyl)amine, tri(hydroxypropyl)amine.
  • the aforedescribed alkanolamines can be present preferably in an amount in the range from 0.01 to 1.0 parts by weight, in particular from 0.1 to 0.5 parts by weight, per 100 parts by weight of polymer.
  • hydrotalcites optionally present in the compositions of the invention can be described by the general formula: [m 2+ 1-x M 3+ x (OH) 2 ] x+ [A n- x/n mH 2 O] x-
  • a n- represents an anion selected from the group consisting of CO 3 2- , OH - , HCO 3- , ClO - 4 ; an acetate ion(-), a salicylate ion(-), a tartrate ion(2-),
  • Preferred hydrotalcites of the invention are those wherein A n- is selected from CO 3 2- , OH - .
  • hydrotalcites can be present in the composition of the invention preferably in an amount from 0.1 to 3 parts by weight, in particular from 0.2 to 1 parts by weight, per 100 parts by weight of PVC.
  • the zeolites optionally present in the compositions of the invention can be described by the general formula: M q/a [(AlO 2 ) q (SiO 2 ) r ] ⁇ wH 2 O
  • the preferred zeolites are described in " Atlas of Zeolite Structure Types", W. M. Meier and D. H. Olson, Butterworths, 3rd Edition, 1992 .
  • zeolites having a particle size mainly in the range from 0.5 to 10 micron.
  • the preferred zeolites which are known per se, have an effective mean cavity diameter of 3-5 ⁇ and can be prepared by known methods.
  • zeolites of type NaA which have an effective mean cavity diameter of 4 ⁇ , and are hence known as 4A zeolites, indicated by the formula: Na 12 Al 12 Si 12 O 48 ⁇ 27H 2 O
  • the zeolites are present preferably in an amount from 0.1 to 3 parts by weight, more preferably from 0.2 to 1 parts by weight, per 100 parts by weight of polymer.
  • polyols optionally present in the composition of the invention, the following are preferred: pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, bistrimethylolethane, trimethylolpropane, inosite, polyvinyl alcohol, sorbitol, maltite, isomaltite, lactite, licasine, mannitol, lactose, leucrose, tris(hydroxyethyl)isocyanurate, palatinite, tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, glycerol, diglycerol, polyglycerol, thiodiglycerol, or 1-0-a-D-glycopyranosyl-D-mannitol dihydrate.
  • TBEIC tris(hydroxyethyl)isocyanurate
  • pentaerythritol dipentaerythritol
  • trimethylolpropane bistrimethylolpropane
  • sorbitol sorbitol.
  • the polyols if present, are present preferably in an amount in the range from 0.01 to 2 parts by weight, more preferably from 0.1 to 1 parts by weight, per 100 parts by weight of PVC.
  • hydrates and oxides of alkali and alkaline-earth metals optionally present in the composition of the invention, the following are preferred: lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide and lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide.
  • the hydrates and oxides of alkali and alkaline-earth metals are preferably in an amount in the range from 0.1 to 3 parts by weight, more preferably from 0.2 to 1 parts by weight, per 100 parts by weight of polymer.
  • the phosphites are preferably organic phosphites of general formula P(OR) 3 , wherein the radicals R are identical or different and can be C 6 -C 18 alkyl, C 6 -C 18 alkenyl, C 5 -C 7 cycloalkyl.
  • acid phosphites of general formula P(OH)R 2 wherein the radicals R are identical or different and selected from C 6 -C 18 alkyl, C 6 -C 18 alkenyl, phenyl, mono- or di-alkylphenyl, or C 5 -C 7 cycloalkyl.
  • Phosphites with the following general formula can also be present: (R 1 O) 2 -PO-R 2 -OP-(OR 3 ) 2 wherein R 1 and R 3 are identical or different and are C 6 -C 18 alkyl, C 6 -C 18 alkenyl, phenyl, mono- or di-alkylphenyl, or C 5 -C 7 cycloalkyl, R 2 is alkyl, alkyloxy, aryl or arylalkyl.
  • Each C 6 -C 18 alkyl substituent present is, for example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl.
  • Preferred are groups having from 8 to 18 carbon atoms.
  • the preferred phosphites in the present invention include: tri(isodecyl)phosphite, tri(nonylphenyl)phosphite, tri(isotridecyl)phosphite, diphenyl isodecyl phosphite, di(isodecyl) phenyl phosphite, di(nonylphenyl) phosphite, tetraphenyl dipropyleneglycol diphosphite, 4,4' isopropylidenediphenol tetra(C 12 - 15 alcohol) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite.
  • the phosphites are preferably in an amount in the range from 0.1 to 2 parts by weight, more preferably from 0.2 to 0.5 parts by weight, per 100 parts by weight of polymer.
  • composition for stabilizing the halogen-containing polymers of the invention if added to the halogen-containing polymer provides the resultant halogenated resin with excellent thermal stability properties, in particular an excellent long-term stability, simultaneously with an excellent initial colour and good retention thereof in the final halogenated resin.
  • the invention hence also concerns a halogenated resin in plasticized or rigid formulation comprising a halogen-containing polymer and a stabilizing composition of the invention.
  • the halogen-containing polymer is polyvinyl chloride PVC, more preferably polyvinyl chloride in rigid form.
  • PVC polyvinyl chloride
  • the stabilizing composition of the invention which comprises disodium adipate, at least one perchlorate salt and one or more stabilizing compounds. Even more preferably, in this embodiment the perchlorate salt is sodium perchlorate.
  • the stabilized halogenated resin preferably stabilized polyvinyl chloride (PVC)
  • PVC polyvinyl chloride
  • the stabilized halogenated resin can be used in formulations for extrusion, injection moulding, blow moulding, calendaring, and can be formed into finished articles such as fibres, ducting, engineering profiles and window profiles, pipes and connectors, film, sheets and bottles.
  • the stabilized rigid polyvinyl chloride resins obtained are advantageously suitable for transparent and non-transparent applications, such as for the production of compact and expanded tubes, profiles and sheets.
  • the halogen-containing polymer is chlorinated polyvinyl chloride (C-PVC).
  • the stabilizing composition of the invention for obtaining stabilized chlorinated polyvinyl chloride (C-PVC) comprises disodium adipate, at least one perchlorate salt and one or more stabilizers. Even more preferably, in said second embodiment the perchlorate salt is sodium perchlorate.
  • halogen-containing polymer can be used to obtain semi-rigid or plasticized halogenated resins.
  • halogen-containing polymer preferably polyvinyl chloride
  • plasticizer substances preferably esters of C 4 -C 20 alcohols such as adipates, phthalates, trimellitates, azelates, sebacates, benzoates, phosphates, epoxidized compounds, typically epoxidized soya oil, polymeric plasticizers such as polyesters, polyadipates, polyphosphates and the like.
  • the plasticizer amount varies widely according to the final use of the plasticized resin, said amount being preferably within the range from 5 to 120 parts by weight per 100 parts by weight of polyvinyl chloride (PVC), more preferably from 20 to 70 parts by weight per 100 parts by weight of PVC.
  • PVC polyvinyl chloride
  • halogen-containing polymer in particular polyvinyl chloride (PVC) or chlorinated polyvinyl chloride (C-PVC) can also be advantageously mixed with other ingredients such as dyes, pigments, antiflame agents, internal or/and external lubricants, impact modifiers, process adjuvants, light and ultraviolet radiation stabilizers, fluorescent whitening agents, fillers, gelling agents, antistatic agents, anti-fogging agents, expanders and other additives to prevent, mask or reduce deterioration caused by heating, ageing and exposure to light.
  • PVC polyvinyl chloride
  • C-PVC chlorinated polyvinyl chloride
  • stabilizing compositions of the invention were prepared, and were added to polyvinyl chloride and additives for the preparation of polyvinyl chloride resins in rigid formulation, these latter then being subjected to static thermal stability tests and Congo Red (CR) thermal stability tests.
  • Static thermal stability of the PVC compositions stabilized with the products of the invention was measured by static thermal stability tests in accordance with the two different methods given below.
  • METHOD 1 Rectangular test samples (1 x 24 cm) were cut from each sheet of thickness 0.1-0.3 mm. The samples were then fixed on the sliding trolley of a temperature-controlled Metrastat dynamic oven. The duration of the test included a pre-heating time.
  • the degree of colour change was judged by reading the yellowness index (YI) according to ASTM D-1925, using an X-Rite QA2000 colorimeter.
  • the yellowness index (YI) corresponded to a number calculated from spectrophotometric data that described the change in colour of a test sample from clear or white towards yellow.
  • METHOD 2 Rectangular test samples 5 x 5 cm in size were cut from each sheet of thickness 0.3-0.5 mm. The samples were then placed in an oven (Ceast WTB Binder) provided with rotating plates and thermostated at 200oC. The samples were then subjected to heating. At regular 10 minute intervals, a sample was taken and the colour change was judged by reading the yellowness index (YI) according to ASTM D-1925, using an X-Rite QA2000 colorimeter.
  • YI yellowness index
  • the thermal stability was also determined by measuring the Congo Red (CR) value.
  • the Congo Red value was obtained in accordance with DIN VDE 0472(614). According to this standard, 50 mg of PVC sample obtained from the sheet were placed in a test-tube and thermostated at 180oC. The time required for the sample to release HCI was then measured by noting the moment wherein the colour change occurred on an indicator paper placed at the top of the test-tube.
  • the ingredients in the amounts indicated in Table 1 were homogeneously mixed to prepare the stabilized rigid PVC formulation of Example 1.
  • the ingredient amounts in Table 1 are expressed in parts by weight per 100 parts by weight of PVC (phr).
  • Formulations 1 and 2 were comparative formulations, while Formulation 3 contained the stabilizing composition of the invention.
  • Table 1 Ingredients of Formulations 1, 2 and 3 Formulation 1 Formulation 2 Formulation 3 INGREDIENTS PVC K67 100 100 100 Calcium carbonate 12 12 12 High impact acrylic 6.5 6.5 6.5 Acrylic processing 0.7 0.7 0.7 aid THEIC* 0.2 0.2 0.2 ARENOX A76** 0.05 0.05 0.05 REALUBE SD*** 0.45 0.45 0.45 Hydroxystearic acid 0.35 0.35 0.35 Polyethylene wax 0.15 0.15 0.15 Oxidized polyethylene wax 0.15 0.15 0.15 0.15 Paraffin wax 0.1 0.1 0.1 Ca Stearate 0.3 0.3 0.3 Zn Stearate 0.3 0.3 0.3 0.3 0.3 Disodium adipate 0.35 - 0.35 60% NaClO 4 in water - 0.05 0.05 *THEIC: polyol **Arenox ® A76: hindered phenolic antioxidant ***Realube SD: distearyl phthalate
  • Formulation 3 of the invention which contained both disodium adipate and sodium perchlorate, showed already initially a high yellowness index value and did not degrade even after 108 minutes of treatment at 190oC.
  • Formulation 2 which contained sodium perchlorate alone, although it initially showed a better yellowness index than Formulation 1, nevertheless always had a YI value lower than Formulation 3 of the invention.
  • Formulation 2 even if at 84 minutes from start of the test showed a yellowness index lower than the formulation of the invention, it, nevertheless, immediately degraded, in contrast to Formulation 3 of the invention which did not degrade even at 108 minutes.
  • Formulation 5 of the invention which comprised both disodium adipate and sodium perchlorate, presented a decidedly lower yellowness index value (YI) than the comparative Formulation 4 over the entire duration of the evaluation period.
  • Formulation 5 of the invention therefore proved to be more stable than the comparative formulation in terms of both greater red congo value and static thermal stability at 200oC. Said increased thermal stability was shown to be extremely advantageous, on the one hand, as it allowed for longer processing times and better colour retention during processing of PVC in rigid formulation, and, on the other hand, it enabled lower amounts of disodium adipate to be used, while achieving better stability.
  • the ingredients in the quantities indicated in Table 5 were homogenously mixed to prepare the stabilized rigid PVC formulation of example 3.
  • the ingredient quantities in Table 5 were expressed in parts by weight, per 100 parts by weight of PVC (phr).
  • Formulations 6 and 7 were comparative Formulations and Formulation 8 contained the stabilizing composition of the invention.
  • Formulation 8 of the invention showed an optimal initial colour and retention thereof up to 50 minutes, compared to Formulation 6 which was already degrading. Comparative Formulation 7 also showed a good initial colour and degraded after 50 minutes, however, it showed a decidedly higher yellowness index than that of the invention as shown in Figure 3 , which gives the static thermal stability data for the three formulations.
  • the ingredients in the amounts indicated in Table 7 were homogeneously mixed to prepare the stabilized rigid C-PVC of Example 4.
  • the ingredient amounts in Table 7 are expressed in parts by weight per 100 parts by weight of C-PVC (phr).
  • Formulation 9 was a comparative formulation and Formulation 10 contained the stabilizing composition of the invention.
  • Table 7 Ingredients of Formulations 9 and 10 Formulation 9 Formulation 10 INGREDIENTS C-PVC 100 100 High impact acrylic 6 6 Polyethylene wax 1 1 Oxidized polyethylene wax 0.5 0.5 TiO 2 4 4 Reatinor RT 403** 1.5 1.5 Disodium adipate 1 0.09 60% NaClO 4 - 0.01 **RT 403: Di butyltin (bis)2-ethylhexyl thioglycolate and Mono butyltin (tris)2-ethylhexyl thioglycolate
  • Formulation 10 of the invention nevertheless showed lower yellowness indices (YI) than comparative Formulation 9, in particular after 50 minutes from the start of the test as is evident from Figure 4 , which gives static thermal stability data for the two formulations.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (23)

  1. Composition pour stabiliser des polymères contenant de l'halogène comprenant :
    a) de l'adipate disodique, et
    b) au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM, M étant sélectionné parmi le groupe constitué de H+, Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Zn2+, Al3+ et NH4 + et k et n sont égaux à 1, 2 ou 3 en fonction de la valence de M, et
    dans laquelle b) n'est pas le perchlorate de baryum.
  2. Composition selon la revendication 1, dans laquelle M de l'au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM est sélectionné parmi le groupe constitué de Li+, Na+, K+, Mg2+, Ca2+ et Zn2+.
  3. Composition selon la revendication 2, dans laquelle M de l'au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM est sélectionné parmi le groupe constitué de Na+, K+ et Ca2+.
  4. Composition selon la revendication 3, dans laquelle M de l'au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM est le sodium.
  5. Composition selon l'une quelconque des revendications 1 à 4, dans laquelle l'au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM est l'acide perchlorique ou un sel de perchlorate.
  6. Composition selon la revendication 5, dans laquelle l'au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM est le perchlorate de sodium.
  7. Composition selon la revendication 5, dans laquelle l'au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM est un complexe de perchlorate de sodium avec le triéthylène glycol, le butyl diglycol ou le polyéthylène glycol.
  8. Composition selon l'une quelconque des revendications 1 à 7, dans laquelle la composition comprend un stabilisant.
  9. Composition selon l'une quelconque des revendications 1 à 8, dans laquelle la composition comprend des co-stabilisants sélectionnés parmi le groupe constitué d'antioxydants, de co-stabilisants organiques (β-dicétones et dihydropyridines ou polydihydropyridines, dérivés d'uracile), d'alcanolamines, de zéolithes et d'hydrotalcites, de polyols, d'hydrates et oxydes de métaux alcalins et alcalino-terreux et de phosphites organiques.
  10. Résine halogénée en formulation rigide comprenant un polymère contenant de l'halogène et une composition stabilisante selon l'une quelconque des revendications 1 à 9.
  11. Résine halogénée selon la revendication 10, dans laquelle le polymère contenant de l'halogène est le poly(chlorure de vinyle) (PVC).
  12. Résine halogénée selon la revendication 10, dans laquelle le polymère contenant de l'halogène est le poly(chlorure de vinyle) chloré (C-PVC).
  13. Résine halogénée en formulation plastifiée ou semi-rigide comprenant un polymère contenant de l'halogène, une substance plastifiante et une composition stabilisante selon l'une quelconque des revendications 1 à 9.
  14. Résine halogénée selon la revendication 13, dans laquelle le polymère contenant de l'halogène est le poly(chlorure de vinyle) (PVC).
  15. Résine halogénée selon l'une quelconque des revendications 10 à 14, dans laquelle la résine comprend des additifs sélectionnés parmi le groupe constitué de colorants, de pigments, d'agents ignifuges, de lubrifiants internes ou/et externes, de modificateurs d'impact, d'adjuvants de traitement, de stabilisants aux rayonnements lumineux et ultraviolets, d'agents de blanchiment fluorescents, de charges, d'agents gélifiants, d'agents antistatiques, d'agents anti-condensation, d'expanseurs et d'autres additifs pour prévenir, masquer ou réduire une détérioration provoquée par un chauffage, un vieillissement et une exposition à la lumière.
  16. Résine halogénée selon l'une quelconque des revendications 10 à 15, dans laquelle l'adipate disodique est présent dans une quantité dans la plage de 0,01 à 5 parties en poids pour 100 parties en poids du polymère contenant de l'halogène.
  17. Résine halogénée selon la revendication 16, dans laquelle l'adipate disodique est présent dans une quantité dans la plage de 0,02 à 2 parties en poids pour 100 parties en poids du polymère contenant de l'halogène.
  18. Résine halogénée selon l'une quelconque des revendications 10 à 17, dans laquelle l'acide perchlorique ou un sel de celui-ci est présent dans une quantité dans la plage de 0,001 à 2 parties en poids pour 100 parties en poids de polymère.
  19. Résine halogénée selon la revendication 18, dans laquelle l'acide perchlorique ou un sel de celui-ci est présent dans une quantité dans la plage de 0,005 à 1 partie en poids pour 100 parties en poids de polymère.
  20. Résine halogénée selon l'une quelconque des revendications 10 à 19, comprenant un ou plusieurs stabilisants dans une quantité dans la plage de 0,05 à 4 parties en poids pour 100 parties en poids de polymère contenant de l'halogène.
  21. Résine halogénée selon l'une quelconque des revendications 10 à 20, comprenant, en tant que stabilisant, un ou plusieurs savons métalliques dans une quantité dans la plage de 0,05 à 3 parties en poids, de préférence de 0,01 à 1,0 partie en poids, pour 100 parties en poids de polymère.
  22. Résine halogénée selon l'une quelconque des revendications 10 à 20, comprenant, en tant que stabilisant, un ou plusieurs composés d'organoétain dans une quantité dans la plage de 0,1 à 4 parties en poids, plus préférentiellement de 0,15 à 2,0 parties en poids, pour 100 parties en poids de polymère.
  23. Utilisation d'une composition comprenant :
    a) de l'adipate disodique, et
    b) au moins un composé sélectionné parmi le groupe constitué de M(ClO4)k et (CF3SO3)nM, M étant sélectionné parmi le groupe constitué de H+, Li+, Na+, K+, Mg2+, Ca2+, Ba2+, Zn2+, Al3+ et NH4+ et k et n sont égaux à 1, 2 ou 3 en fonction de la valence de M ;
    pour stabiliser des polymères contenant de l'halogène.
EP09151014.9A 2008-01-23 2009-01-21 Composition pour stabiliser des polymères contenant de l'halogène Active EP2083044B1 (fr)

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IT000097A ITMI20080097A1 (it) 2008-01-23 2008-01-23 Composizione per la stabilizzazione di polimeri contenenti alogeno

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EP2363431A1 (fr) * 2010-02-25 2011-09-07 Reagens S.p.A. Composition comprenant des carboxylates de sodium pour stabiliser des polymères contenant un halogène
WO2012143794A1 (fr) 2011-04-18 2012-10-26 Galata Chemicals Gmbh Système stabilisateur de polymères pour polymères halogénés
CN103910918B (zh) * 2013-01-06 2016-08-24 临安华立塑胶有限公司 一种微发泡木塑专用环保钙锌复合稳定剂组分及生产方法
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CN105209532B (zh) * 2013-03-15 2017-11-28 路博润先进材料公司 不含重金属的cpvc组合物
DE102013005426A1 (de) * 2013-03-27 2014-10-02 Baerlocher Gmbh Stabilisatorzusammensetzungen enthaltend Salze von Dicarbonsäuren und Polyole
CN105647051A (zh) * 2014-11-12 2016-06-08 吉林吉瑞莱板材科技有限公司 一种硅藻土钙塑合板材及其生产方法
CN104910555B (zh) * 2015-06-08 2017-07-28 湖北南星化工总厂 一种二元羧酸碱金属盐作为锌烧抑制剂的应用
CN105623142A (zh) * 2015-07-13 2016-06-01 惠州市金浩润电业有限公司 一种高稳定性硬质pvc胶粒的制备方法
CN105566806A (zh) * 2016-01-27 2016-05-11 安徽天龙电器线缆集团有限公司 一种低烟环保耐油绝缘电缆配方
CN105647066A (zh) * 2016-03-30 2016-06-08 苗庆龄 一种耐磨阻燃电缆料及制备方法
CN105885292A (zh) * 2016-05-19 2016-08-24 安徽省无为县佳和电缆材料有限公司 一种通讯电缆护套料
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